Phosphoryl radical-initiated Atherton–Todd-type …S1 Phosphoryl radical-initiated Atherton–Todd-type reaction under open air Yingcong Ou,a Yuanting Huang,a Zhenlin He,a Guodian

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Phosphoryl radical-initiated Atherton–Todd-type reaction under

open air

Yingcong Ou,a Yuanting Huang,a Zhenlin He,a Guodian Yu,a Yanping Huo,a Xianwei

Li,a Yang Gao,a and Qian Chen*a,b

aSchool of Chemical Engineering and Light Industry, Guangdong University of

Technology, Guangzhou 510006, China

bKey Laboratory of Functional Molecular Engineering of Guangdong Province, South

China University of Technology, Guangzhou 510640, China

*[email protected]

SUPPORTING INFORMATION

Content:

1. General Information……………………………………………………………..S2

2. Overview of Substrates Numbering…………………………………………..…S3

3. Mechanistic Studies………………………...…………………………………...S4

4. Experimental Section……………………………………………………………S9

5. Analytic Data for Products…………………………………………………..…S11

6. NMR Spectra for Products……………………………………………………..S29

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2019

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1. General Information

Unless otherwise stated, commercially available reagents including dry solvents

were used without additional purification. Petroleum ether refers to the petroleum

fraction b.p. 60−90 °C. Secondary phosphine oxides which were not commercially

available were prepared according to the literature.1 All reactions were carried out in

oven-dried thick-walled glassware. Flash chromatography was performed using the

indicated solvent system on silica gel standard grade (200−300 mesh). 1H NMR

spectra were recorded in CDCl3 on a Bruker 400 (400 MHz) spectrometer. 13C NMR

spectra were recorded in CDCl3 on a Bruker 400 (100 MHz) spectrometer. 31P NMR

spectra were recorded in CDCl3 on a Bruker 400 (162 MHz) spectrometer. 19F NMR

spectra were recorded in CDCl3 on a Bruker 400 (376 MHz) spectrometer. Chemical

shifts were reported relative to CDCl3 (δ 7.26 ppm) for 1H NMR and CDCl3 (δ 77.16

ppm) for 13C NMR. High-resolution mass spectra (HRMS) were recorded on an

Q-Exactive Orbitrap mass spectrometer (Thermo, CA). Abbreviations for signal

coupling are as follows: s = singlet, d = doublet; t = triplet, q = quartet, dd = doublet

of doublets, m = multiplet, br = broad.

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2. Overview of Substrates Numbering

S4

3. Mechanistic Studies

1) The Investigation of the Effect of Air Atmosphere

To a solution of diphenylphosphine oxide 1a (40 mg, 0.2 mmol) and ethanol 2a (46

mg, 1 mmol) in PEG-200 (2 mL) were added CHCl3 (24 mg, 0.2 mmol) and DBU (46

mg, 0.3 mmol). The mixture was stirred at 25 oC under N2 for 3 h. The reaction

mixture was quenched with saturated aqueous NaCl solution (20 mL), and the

resulting mixture was then extracted with ethyl acetate (3×20 mL). The combined

organic layers were dried over anhydrous Na2SO4 and concentrated under reduced

pressure. The desired ethyl diphenylphosphinate 3aa was not detected from 1H NMR

spectrum of the crude mixture.

2) The Investigation of the Effect of Visible Light


mg, 1 mmol) in PEG-200 (2 mL) were added CHCl3 (24 mg, 0.2 mmol) and DBU (46

mg, 0.3 mmol). The mixture was stirred at 25 oC under air atmosphere in the dark for

3 h. The reaction mixture was quenched with saturated aqueous NaCl solution (20

mL), and the resulting mixture was then extracted with ethyl acetate (3×20 mL). The

combined organic layers were dried over anhydrous Na2SO4 and concentrated under

reduced pressure. The crude product was purified by flash column chromatography on

silica gel with petroleum ether/ethyl acetate (2:1) to afford ethyl diphenylphosphinate

3aa (48 mg, 98%) as a colorless oil.

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3) The Investigation of By-Products

To a solution of diphenylphosphine oxide 1a (10 mg, 0.05 mmol) and ethanol 2a

(12 mg, 0.25 mmol) in CD3CN (0.5 mL) were added CHCl3 (6 mg, 0.05 mmol) and

DBU (12 mg, 0.075 mmol). The mixture was stirred at 25 oC under air atmosphere for

3 h. The by-product CH2Cl2 with 90% yield was detected from 1H NMR spectrum of

the resulting mixture according to the yield of 3aa (99%).

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4) Radical-Trapping Experiment

To a solution of diphenylphosphine oxide 1a (40 mg, 0.2 mmol) and the radical

scavenger diphenylethene 6 (72 mg, 0.4 mmol) in CH3CN (2 mL) were added CHCl3

(24 mg, 0.2 mmol) and DBU (46 mg, 0.3 mmol). The mixture was stirred at 25 oC

under air atmosphere for 3 h. The reaction mixture was then concentrated under

reduced pressure. The adducts 7 and 8, which should be generated via a phosphoryl

radical pathway, were detected by LC-MS spectrum of the crude mixture.

O

PPh H

Ph1a

+

TEMPO(2 equiv)

open airCHCl3 (1 equiv)

DBU (1.5 equiv)

CH3CN, 25 oC, 3 h

detected by LC-MS

N

OP

Ph

Ph

O

N

O

To a solution of diphenylphosphine oxide 1a (40 mg, 0.2 mmol) and the radical

scavenger TEMPO (62 mg, 0.4 mmol) in CH3CN (2 mL) were added CHCl3 (24 mg,

0.2 mmol) and DBU (46 mg, 0.3 mmol). The mixture was stirred at 25 oC under air

atmosphere for 3 h. The reaction mixture was then concentrated under reduced

PhPh

7

[M - H]+ = 397.14

P

OPh

Ph

OH

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pressure. The TEMPO-P(O)Ph2 adduct was detected by LC-MS spectrum of the crude

mixture, suggesting that a phosphoryl radical reaction pathway might be involved.

To a solution of diphenylphosphine oxide 1a (40 mg, 0.2 mmol), ethanol 2a (46 mg,

1 mmol) and the radical scavenger BQ (43 mg, 0.4 mmol) in CH3CN (2 mL) were

added CHCl3 (24 mg, 0.2 mmol) and DBU (46 mg, 0.3 mmol). The mixture was

stirred at 25 oC under air atmosphere for 3 h. The reaction mixture was then

concentrated under reduced pressure. The desired reaction of 1a with 2a was

completely inhibited, and the BQ-P(O)Ph2 adduct was detected by LC-MS spectrum

of the crude mixture, suggesting that a radical reaction pathway might be involved.

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5) The Investigation of the Effect of Catalytic Amounts of O2


mg, 1 mmol) in CH3CN (2 mL) were added CHCl3 (24 mg, 0.2 mmol), DBU (46 mg,

0.3 mmol), and O2 (1.8 mL, 0.08 mmol) under N2. The mixture was stirred at 25 oC

for 3 h. The reaction mixture was then concentrated under reduced pressure. The

crude product was purified by flash column chromatography on silica gel with

petroleum ether/ethyl acetate (2:1) to afford ethyl diphenylphosphinate 3aa (45 mg,

92%) as a colorless oil.

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4. Experimental Section

1) General Procedure for the Atherton–Todd-Type Reaction in CH3CN


mg, 1 mmol) in CH3CN (2 mL) were added CHCl3 (24 mg, 0.2 mmol) and DBU (46

mg, 0.3 mmol). The mixture was stirred at 25 oC under air atmosphere for 3 h (Figure

S1). The reaction mixture was then concentrated under reduced pressure. The crude

product was purified by flash column chromatography on silica gel with petroleum

ether/ethyl acetate (2:1) to afford ethyl diphenylphosphinate 3aa (48 mg, 98%) as a

colorless oil.

Figure S1 The reaction setup for the general procedure.

2) General Procedure for the Atherton–Todd-Type Reaction in PEG-200

To a solution of bis(4-methoxyphenyl)phosphine oxide 1b (52 mg, 0.2 mmol) and

methanol 2b (32 mg, 1 mmol) in PEG-200 (2 mL) were added CHCl3 (24 mg, 0.2

S10

mmol) and DBU (46 mg, 0.3 mmol). The mixture was stirred at 25 oC under air

atmosphere for 3 h (Figure S1). The reaction mixture was quenched with saturated

aqueous NaCl solution (20 mL), and the resulting mixture was then extracted with

ethyl acetate (3×20 mL). The combined organic layers were dried over anhydrous

Na2SO4 and concentrated under reduced pressure. The crude product was purified by

flash column chromatography on silica gel with petroleum ether/ethyl acetate (2:1) to

afford methyl bis(4-methoxyphenyl)phosphinate 3bb (58 mg, 99%) as a colorless oil.

3) Large-Scale Synthesis

To a solution of diphenylphosphine oxide 1a (20.22 g, 0.10 mol) and ethanol 2a

(23.04 g, 0.50 mol) in PEG-200 (100 mL) were added CHCl3 (11.94 g, 0.10 mol) and

DBU (22.84 g, 0.15 mol). The mixture was stirred at 25 oC under air atmosphere for 3

h. The reaction mixture was quenched with saturated aqueous NaCl solution (1 L),

and the resulting mixture was then extracted with ethyl acetate (3×1 L). The combined

organic layers were dried over anhydrous Na2SO4 and concentrated under reduced

pressure. The crude product was purified by flash column chromatography on silica

gel with petroleum ether/ethyl acetate (2:1) to afford ethyl diphenylphosphinate 3aa

(18.47 g, 75%) as a colorless oil.

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5. Analytic Data for Products

The known compounds 3aa,2 3ab,2 3ac,2 3ad,2 3ae,2 3af,3 3ag,3 3ah,3 3ai,4 3aj,2

3ak,3 3an,5 3ao,5 3ap,6 3ar,6 3as,7 3at,7 3au,7 3av,6 3bb,2 3cb,2 3eb,2 3fb,2 3gb,2

3hb,8 3ib,2 3kb,2 3mb,2 3ob,2 5a,9 5b,10 5c,11 5d,12 5e,13 5f,14 5h,15 5i,15 5j,16 and 5l16

showed characterization data in full agreement with previously reported data.

Ethyl Diphenylphosphinate (3aa)2.

Colorless oil (48 mg, 98%): 1H NMR (400 MHz, CDCl3) δ 7.84−7.77 (m, 4H),

7.53−7.47 (m, 2H), 7.46−7.40 (m, 4H), 4.14−4.05 (m, 2H), 1.36 (t, J = 7.1 Hz, 3H);

13C NMR (100 MHz, CDCl3) δ 132.1 (d, J = 2.8 Hz), 131.7 (d, J = 136 Hz), 131.6 (d,

J = 10.1 Hz), 128.5 (d, J = 13.1 Hz), 61.1 (d, J = 5.9 Hz), 16.5 (d, J = 6.7 Hz); 31P

NMR (162 MHz, CDCl3) δ 31.4.

Methyl Diphenylphosphinate (3ab)2.


7.55−7.49 (m, 2H), 7.48−7.41 (m, 4H), 3.76 (d, J = 11.1 Hz, 3H); 13C NMR (100

MHz, CDCl3) δ 132.2 (d, J = 2.8 Hz), 131.7 (d, J = 10.1 Hz), 131.1 (d, J = 136 Hz),

128.6 (d, J = 13.1 Hz), 51.5 (d, J = 6.0 Hz); 31P NMR (162 MHz, CDCl3) δ 33.3.

Propyl Diphenylphosphinate (3ac)2.

Colorless oil (48 mg, 92％): 1H NMR (400 MHz, CDCl3) δ 7.86−7.76 (m, 4H),

7.55−7.48 (m, 2H), 7.47−7.42 (m, 4H), 3.99 (q, J = 6.7 Hz, 2H), 1.79−1.70 (m, 2H),

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0.98 (t, J = 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 132.1 (d, J = 2.8 Hz), 131.7

(d, J = 137 Hz), 131.6 (d, J = 10.1 Hz), 128.5 (d, J = 13.1 Hz), 66.5 (d, J = 6.1 Hz),

23.9 (d, J = 6.7 Hz), 10.2; 31P NMR (162 MHz, CDCl3) δ 31.1.

Butyl Diphenylphosphinate (3ad)2.


7.53−7.38 (m, 6H), 4.01 (q, J = 6.6 Hz, 2H), 1.79−1.62 (m, 2H), 1.47−1.37 (m, 2H),



32.6 (d, J = 6.7 Hz), 18.9, 13.6; 31P NMR (162 MHz, CDCl3) δ 31.1.

Pentyl Diphenylphosphinate (3ae)2.


7.56−7.38 (m, 6H), 4.01 (q, J = 6.7 Hz, 2H), 1.75−1.68 (m, 2H), 1.44−1.25 (m, 4H),



30.2 (d, J = 6.6 Hz), 27.8, 22.2, 13.9; 31P NMR (162 MHz, CDCl3) δ 31.2.

Phenethyl Diphenylphosphinate (3af)3.


7.51−7.44 (m, 2H), 7.42−7.34 (m, 4H), 7.30−7.15 (m, 5H), 4.20 (q, J = 6.8 Hz, 2H),

3.02 (t, J = 6.9 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 137.5, 132.1 (d, J = 2.8 Hz),

131.6 (d, J = 10.2 Hz), 131.3 (d, J = 136 Hz), 129.1, 128.6, 128.5 (d, J = 4.9 Hz),

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126.6, 65.4 (d, J = 6.0 Hz), 37.1 (d, J = 7.0 Hz); 31P NMR (162 MHz, CDCl3) δ 31.6.

Benzyl Diphenylphosphinate (3ag)3.


7.54−7.50 (m, 2H), 7.47−7.42 (m, 4H), 7.39−7.28 (m, 5H), 5.07 (d, J = 6.8 Hz, 2H);

13C NMR (100 MHz, CDCl3) δ 136.4 (d, J = 7.5 Hz), 132.2 (d, J = 2.8 Hz), 131.7 (d,

J = 10.2 Hz), 131.3 (d, J = 137 Hz), 128.6 (d, J = 13.1 Hz), 128.5, 128.2, 127.8, 66.3

(d, J = 5.5 Hz); 31P NMR (162 MHz, CDCl3) δ 32.4.

Allyl Diphenylphosphinate (3ah)3.


7.54−7.47 (m, 2H), 7.47−7.36 (m, 4H), 6.03−5.88 (m, 1H), 5.37−5.32 (m, 1H),

5.23−5.19 (m, 1H), 4.54−4.50 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 133.0 (d, J =

7.3 Hz), 132.2 (d, J = 2.8 Hz), 131.6 (d, J = 10.2 Hz), 131.4 (d, J = 137 Hz), 128.6 (d,

J = 13.2 Hz), 117.9, 65.3 (d, J = 5.5 Hz); 31P NMR (162 MHz, CDCl3) δ 32.2.

Prop-2-yn-1-yl Diphenylphosphinate (3ai)4.


7.53−7.46 (m, 2H), 7.44−7.40 (m, 4H), 4.66 (dd, J = 6.8, 2.4 Hz, 2H), 2.47 (t, J = 2.5

Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 132.5 (d, J = 2.8 Hz), 131.7 (d, J = 10.4 Hz),

130.7 (d, J = 137 Hz), 128.6 (d, J = 13.3 Hz), 78.0 (d, J = 8.9 Hz), 75.8, 52.4 (d, J =

4.6 Hz); 31P NMR (162 MHz, CDCl3) δ 34.1.

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Isopropyl Diphenylphosphinate (3aj)2.

Colorless oil (21 mg, 41%): 1H NMR (400 MHz, CDCl3) δ 7.85−7.77 (m, 4H), 7.53−

7.46 (m, 2H), 7.46−7.39 (m, 4H), 4.73−4.60 (m, 1H), 1.34 (d, J = 6.1 Hz, 6H); 13C

NMR (100 MHz, CDCl3) δ 132.4 (d, J = 136 Hz), 131.9 (d, J = 2.7 Hz), 131.6 (d, J =

10.1 Hz), 128.4 (d, J = 13.1 Hz), 70.2 (d, J = 6.0 Hz), 24.3 (d, J = 4.2 Hz); 31P NMR

(162 MHz, CDCl3) δ 29.8.

Cyclohexyl Diphenylphosphinate (3ak)3.


7.53−7.38 (m, 6H), 4.46−4.37 (m, 1H), 1.90−1.87 (m, 2H), 1.77−1.67 (m, 2H),

1.67−1.54 (m, 2H), 1.51−1.40 (m, 1H), 1.35−1.18 (m, 3H); 13C NMR (100 MHz,

CDCl3) δ 132.6 (d, J = 137 Hz), 131.9 (d, J = 2.8 Hz), 131.6 (d, J = 10.1 Hz), 128.4 (d,

J = 13.1 Hz), 75.0 (d, J = 6.1 Hz), 33.9 (d, J = 3.6 Hz), 25.2, 23.6; 31P NMR (162

MHz, CDCl3) δ 29.7.

(3S,5S,8R,9S,10S,13R,14S,17R)-10,13-Dimethyl-17-((R)-6-methylheptan-2-yl)hex

adecahydro-1H-cyclopenta[a]phenanthren-3-yl Diphenylphosphinate (3al).

White amorphous solid (47 mg, 40%): 1H NMR (400 MHz, CDCl3) δ 7.86−7.75 (m,

4H), 7.53−7.39 (m, 6H), 4.37−4.27 (m, 1H), 1.98−1.85 (m, 3H), 1.84−0.93 (m, 28H),

0.88 (d, J = 6.5 Hz, 3H), 0.86 (d, J = 1.8 Hz, 3H), 0.84 (d, J = 1.8 Hz, 3H), 0.82 (s,

3H), 0.63 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 132.6 (d, J = 135 Hz), 132.5 (d, J =

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135 Hz), 131.9 (d, J = 2.6 Hz), 131.6 (d, J = 10.0 Hz), 131.6 (d, J = 10.0 Hz), 128.4 (d,

J = 13.0 Hz), 76.2 (d, J = 6.3 Hz), 56.3 (d, J = 13.9 Hz), 54.2, 44.7, 42.6, 40.0, 39.5,

36.8, 36.6 (d, J = 3.5 Hz), 36.2, 35.8, 35.4, 35.3, 31.9, 30.1 (d, J = 3.8 Hz), 28.5, 28.2,

28.0, 24.2, 23.8, 22.8, 22.6, 21.2, 18.7, 12.3, 12.1; 31P NMR (162 MHz, CDCl3) δ

29.9; HRMS (ESI-Orbitrap) m/z: [M + Na]+ calcd for C39H57O2PNa 611.3981, found

611.3989.

Phenyl Diphenylphosphinate (3an)5.


4H), 7.60−7.43 (m, 6H), 7.29−7.22 (m, 4H), 7.15−7.05 (m, 1H); 13C NMR (100 MHz,

CDCl3) δ 150.9 (d, J = 8.2 Hz), 132.4 (d, J = 2.9 Hz), 131.8 (d, J = 10.4 Hz), 131.0 (d,

J = 138 Hz), 129.6, 128.6 (d, J = 13.5 Hz), 124.6, 120.7 (d, J = 4.8 Hz); 31P NMR

(162 MHz, CDCl3) δ 30.4.

4-Methoxyphenyl Diphenylphosphinate (3ao)5.


4H), 7.55−7.47 (m, 2H), 7.47−7.40 (m, 4H), 7.10 (dd, J = 9.1, 1.2 Hz, 2H), 6.73 (d, J

= 9.0 Hz, 2H), 3.69 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 156.4, 144.3 (d, J = 8.4

Hz), 132.5 (d, J = 2.8 Hz), 131.8 (d, J = 10.4 Hz), 130.9 (d, J = 138 Hz), 128.6 (d, J =

13.4 Hz), 121.7 (d, J = 4.5 Hz), 114.6, 55.5; 31P NMR (162 MHz, CDCl3) δ 30.7.

3-Methoxyphenyl Diphenylphosphinate (3ap)6.

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7.58−7.50 (m, 2H), 7.50−7.41 (m, 4H), 7.11 (dd, J = 8.4, 8.0 Hz, 1H), 6.82−6.73 (m,

2H), 6.66−6.59 (m, 1H), 3.71 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 160.6, 151.8 (d,

J = 8.0 Hz), 132.5 (d, J = 2.8 Hz), 131.8 (d, J = 10.4 Hz), 131.0 (d, J = 138 Hz), 129.9,

128.6 (d, J = 13.5 Hz), 112.9 (d, J = 4.7 Hz), 110.7, 106.7 (d, J = 5.1 Hz), 55.4; 31P

NMR (162 MHz, CDCl3) δ 31.0.

3,4-Dimethoxyphenyl Diphenylphosphinate (3aq).


7.58−7.40 (m, 6H), 6.75 (s, 1H), 6.70−6.66 (m, 2H), 3.78 (s, 3H), 3.75 (s, 3H); 13C

NMR (100 MHz, CDCl3) δ 149.4, 146.0, 144.5 (d, J = 8.4 Hz), 132.4 (d, J = 2.9 Hz),

131.8 (d, J = 10.3 Hz), 130.9 (d, J = 138 Hz), 128.6 (d, J = 13.4 Hz), 112.0 (d, J = 4.7

Hz), 111.4, 105.4 (d, J = 4.5 Hz), 56.1, 55.9; 31P NMR (162 MHz, CDCl3) δ 30.6;

HRMS (ESI-Orbitrap) m/z: [M + Na]+ calcd for C20H19O4PNa 377.0913, found

377.0908.

m-Tolyl Diphenylphosphinate (3ar)6.

Yellow oil (61 mg, 99%): 1H NMR (400 MHz, CDCl3) δ 7.96−7.82 (m, 4H),

7.54−7.48 (m, 2H), 7.48−7.40 (m, 4H), 7.11−7.07 (m, 1H), 7.05 (s, 1H), 6.97 (d, J =

8.2 Hz, 1H), 6.87 (d, J = 7.5 Hz, 1H), 2.25 (s, 3H); 13C NMR (100 MHz, CDCl3) δ

150.8 (d, J = 8.3 Hz), 139.9, 132.4 (d, J = 2.8 Hz), 131.8 (d, J = 10.3 Hz), 131.1 (d, J

= 138 Hz), 129.3, 128.6 (d, J = 13.4 Hz), 125.4, 121.4 (d, J = 4.8 Hz), 117.6 (d, J =

4.8 Hz), 21.3; 31P NMR (162 MHz, CDCl3) δ 30.1.

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3,4-Dimethylphenyl Diphenylphosphinate (3as)7.


4H), 7.54−7.38 (m, 6H), 7.02 (s, 1H), 6.95 (d, J = 8.2 Hz, 1H), 6.90 (d, J = 8.3 Hz,

1H), 2.15 (s, 3H), 2.12 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 148.8 (d, J = 8.3 Hz),

138.1, 132.8, 132.3 (d, J = 2.8 Hz), 131.8 (d, J = 10.3 Hz), 131.3 (d, J = 138 Hz),

130.4, 128.5 (d, J = 13.4 Hz), 121.8 (d, J = 4.7 Hz), 117.7 (d, J = 4.7 Hz), 19.8, 19.0;

31P NMR (162 MHz, CDCl3) δ 29.9.

4-Bromophenyl Diphenylphosphinate (3at)7.


4H), 7.59−7.51 (m, 2H), 7.50−7.42 (m, 4H), 7.37−7.30 (m, 2H), 7.13−7.05 (m, 2H);

13C NMR (100 MHz, CDCl3) δ 150.0 (d, J = 8.2 Hz), 132.7, 132.6, 131.8 (d, J = 10.4

Hz), 130.5 (d, J = 138 Hz), 128.7 (d, J = 13.5 Hz), 122.5 (d, J = 4.8 Hz), 117.6 (d, J =

1.1 Hz); 31P NMR (162 MHz, CDCl3) δ 31.3.

4-Chlorophenyl Diphenylphosphinate(3au)7.


4H), 7.62−7.41 (m, 6H), 7.23−7.17 (m, 2H), 7.15−7.13 (m, 2H); 13C NMR (100 MHz,


J = 138 Hz), 129.7, 128.7 (d, J = 13.5 Hz), 122.1 (d, J = 4.8 Hz), 116.8; 31P NMR

(162 MHz, CDCl3) δ 31.3.

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Naphthalen-2-yl Diphenylphosphinate (3av)6.


4H), 7.77−7.66 (m, 4H), 7.56−7.31 (m, 9H); 13C NMR (100 MHz, CDCl3) δ 148.6 (d,

J = 8.4 Hz), 133.9, 132.5 (d, J = 2.8 Hz), 131.9, 131.8, 130.9 (d, J = 138 Hz), 130.7,

129.8, 128.7 (d, J = 13.5 Hz), 127.6 (d, J = 10.0 Hz), 126.6, 125.3, 120.7 (d, J = 4.9

Hz), 117.2 (d, J = 5.1 Hz); 31P NMR (162 MHz, CDCl3) δ 30.8.

2,3-Dihydroxypropyl Diphenylphosphinate and 1,3-Dihydroxypropan-2-yl

Diphenylphosphinate (3aw).

Colorless oil (56 mg, 96%), two isomers in ∼15:1 ratio: 1H NMR (400 MHz, CDCl3)

major product: δ 7.85−7.75 (m, 4H), 7.60−7.51 (m, 2H), 7.50−7.41 (m, 4H), 4.11 (dd,

J = 11.0, 5.0 Hz, 2H), 3.97−3.93 (m, 1H), 3.71 (d, J = 4.7 Hz, 2H), 2.84 (br, 2H); 13C

NMR (100 MHz, CDCl3) major product: δ 132.7 (d, J = 2.7 Hz), 132.6 (d, J = 2.6 Hz),

131.7 (d, J = 10.3 Hz), 131.6 (d, J = 10.3 Hz), 130.2 (d, J = 138 Hz), 130.1 (d, J =

137 Hz), 128.8 (d, J = 13.3 Hz), 128.7 (d, J = 13.3 Hz), 70.8 (d, J = 3.4 Hz), 67.2 (d, J

= 6.3 Hz), 62.7; 31P NMR (162 MHz, CDCl3) major product: δ 36.2; HRMS

(ESI-Orbitrap) m/z: [M + Na]+ calcd for C15H17O4PNa 315.0757, found 315.0755.

Methyl Bis(4-methoxyphenyl)phosphinate (3bb)2.

Colorless oil (58 mg, 99%): 1H NMR (400 MHz, CDCl3) δ 7.70 (dd, J = 11.7, 8.5 Hz,

4H), 6.93 (dd, J = 8.7, 2.5 Hz, 4H), 3.81 (s, 6H), 3.70 (d, J = 11.2 Hz, 3H); 13C NMR

(100 MHz, CDCl3) δ 162.5 (d, J = 3.1 Hz), 133.4 (d, J = 11.4 Hz), 122.7 (d, J = 145

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Hz), 114.0 (d, J = 14.2 Hz), 55.3, 51.2 (d, J = 5.9 Hz); 31P NMR (162 MHz, CDCl3) δ

34.0.

Methyl Di-p-tolylphosphinate (3cb)2.


4H), 7.25 (dd, J = 7.7, 2.4 Hz, 4H), 3.73 (d, J = 11.1 Hz, 3H), 2.37 (s, 6H); 13C NMR

(100 MHz, CDCl3) δ 142.6 (d, J = 2.9 Hz), 131.6 (d, J = 10.5 Hz), 129.2 (d, J = 13.5

Hz), 127.9 (d, J = 140 Hz), 51.4 (d, J = 6.0 Hz), 21.6; 31P NMR (162 MHz, CDCl3) δ

34.3.

Methyl Di([1,1'-biphenyl]-4-yl)phosphinate (3db).

White amorphous solid (65 mg, 85%): 1H NMR (400 MHz, CDCl3) δ 7.94 (dd, J =

11.9, 8.3 Hz, 4H), 7.70 (dd, J = 8.3, 3.2 Hz, 4H), 7.63−7.56 (m, 4H), 7.48−7.42 (m,

4H), 7.41−7.35 (m, 2H), 3.83 (d, J = 11.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ

144.9 (d, J = 2.9 Hz), 139.8, 132.1 (d, J = 10.5 Hz), 129.5 (d, J = 139 Hz), 128.8,

128.0, 127.3, 127.1, 51.5 (d, J = 6.0 Hz); 31P NMR (162 MHz, CDCl3) δ 33.3; HRMS


Methyl Bis(4-chlorophenyl)phosphinate (3eb)2.

S20

Yellow oil (57 mg, 95％): 1H NMR (400 MHz, CDCl3) δ 7.76−7.68 (m, 4H),

7.47−7.40 (m, 4H), 3.76 (d, J = 11.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 139.1

(d, J = 3.5 Hz), 133.0 (d, J = 11.0 Hz), 129.2 (d, J = 139 Hz), 129.1 (d, J = 13.8 Hz),

51.7 (d, J = 6.0 Hz); 31P NMR (162 MHz, CDCl3) δ 31.2.

Methyl Bis(4-fluorophenyl)phosphinate (3fb)2.

Colorless oil (50 mg, 94％): 1H NMR (400 MHz, CDCl3) δ 7.83−7.71 (m, 4H),

7.16−7.09 (m, 4H), 3.73 (d, J = 11.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 165.2

(dd, J = 254, 3.5 Hz), 134.1 (dd, J = 11.5, 8.9 Hz), 126.8 (dd, J = 142, 3.4 Hz), 116.0

(dd, J = 21.4, 14.4 Hz), 51.5 (d, J = 6.0 Hz); 31P NMR (162 MHz, CDCl3) δ 31.3; 19F

NMR (376 MHz, CDCl3) δ -105.9 (d, J = 1.2 Hz).

Methyl Bis(4-(trifluoromethyl)phenyl)phosphinate (3gb)2.


4H), 7.73 (dd, J = 8.2, 2.6 Hz, 4H), 3.82 (d, J = 11.2 Hz, 3H); 13C NMR (100 MHz,

CDCl3) δ 134.6 (d, J = 137 Hz), 134.4 (dd, J = 32.8, 3.1 Hz), 132.2 (d, J = 10.5 Hz),

125.7 (dq, J = 13.3, 3.7 Hz), 123.4 (d, J = 272 Hz), 52.0 (d, J = 6.0 Hz); 31P NMR

(162 MHz, CDCl3) δ 29.3; 19F NMR (376 MHz, CDCl3) δ -63.4.

S21

Methyl Bis(3-methoxyphenyl)phosphinate (3hb)8.


7.08−7.02 (m, 2H), 3.82 (s, 6H), 3.77 (d, J = 11.2 Hz, 3H); 13C NMR (100 MHz,

CDCl3) δ 159.6 (d, J = 16.5 Hz), 132.3 (d, J = 135 Hz), 129.8 (d, J = 15.5 Hz), 123.8

(d, J = 9.8 Hz), 118.5 (d, J = 2.8 Hz), 116.4 (d, J = 11.3 Hz), 55.4, 51.6 (d, J = 6.1

Hz); 31P NMR (162 MHz, CDCl3) δ 33.2.

Methyl Di-m-tolylphosphinate (3ib)2.

Colorless oil (47 mg, 91％): 1H NMR (400 MHz, CDCl3) δ 7.62 (d, J = 12.7 Hz, 2H),

7.55 (dd, J = 12.7, 5.6 Hz, 2H), 7.33−7.26 (m, 4H), 3.72 (d, J = 11.1 Hz, 3H), 2.34 (s,

6H); 13C NMR (100 MHz, CDCl3) δ 138.3 (d, J = 13.1 Hz), 132.8 (d, J = 2.9 Hz),

132.0 (d, J = 10.1 Hz), 130.8 (d, J = 136 Hz), 128.5 (d, J = 10.0 Hz), 128.3 (d, J =

13.8 Hz), 51.4 (d, J = 6.1 Hz), 21.2; 31P NMR (162 MHz, CDCl3) δ 33.9.

Methyl Bis(3-fluorophenyl)phosphinate (3jb).


7.53−7.38 (m, 4H), 7.26−7.20 (m, 2H), 3.78 (d, J = 9.8 Hz, 3H); 13C NMR (100 MHz,

CDCl3) δ 162.6 (dd, J = 250, 18.7 Hz), 133.2 (dd, J = 138, 5.6 Hz), 130.8 (dd, J =

15.4, 7.4 Hz), 127.4 (dd, J = 9.5, 3.2 Hz), 119.7 (dd, J = 21.2, 2.3 Hz), 118.5 (dd, J =

S22

22.3, 10.8 Hz), 51.9 (d, J = 5.9 Hz); 31P NMR (162 MHz, CDCl3) δ 29.9; 19F NMR

(376 MHz, CDCl3) δ -110.9 (d, J = 5.6 Hz); HRMS (ESI-Orbitrap) m/z: [M + Na]+

calcd for C13H11F2O2PNa 291.0357, found 291.0353.

Methyl Di-o-tolylphosphinate (3kb)2.


2H), 7.41 (dd, J = 7.4, 7.4 Hz, 2H), 7.33−7.24 (m, 2H), 7.24−7.13 (m, 2H), 3.75 (d, J

= 11.8 Hz, 3H), 2.35 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 141.7 (d, J = 11.1 Hz),

133.6 (d, J = 10.0 Hz), 132.3 (d, J = 2.7 Hz), 131.4 (d, J = 12.6 Hz), 129.5 (d, J = 133

Hz), 125.5 (d, J = 12.7 Hz), 51.0 (d, J = 5.9 Hz), 21.1 (d, J = 4.2 Hz); 31P NMR (162

MHz, CDCl3) δ 34.2.

Methyl Bis(3,5-dimethoxyphenyl)phosphinate (3lb).


4H), 6.54 (dd, J = 2.3, 2.3 Hz, 2H), 3.75 (s, 12H), 3.73 (d, J = 11.2 Hz, 3H); 13C NMR

(100 MHz, CDCl3) δ 160.8 (d, J = 19.6 Hz), 132.5 (d, J = 137 Hz), 109.0 (d, J = 11.2

Hz), 104.5 (d, J = 2.5 Hz), 55.4, 51.6 (d, J = 6.0 Hz); 31P NMR (162 MHz, CDCl3) δ

33.5; HRMS (ESI-Orbitrap) m/z: [M + Na]+ calcd for C17H21O6PNa 375.0968, found

375.0963.

S23

Methyl Bis(3,5-dimethylphenyl)phosphinate (3mb)2.

Colorless oil (55 mg, 95%): 1H NHR (400 MHz, CDCl3) δ 7.42 (d, J = 12.5 Hz, 4H),

7.14 (s, 2H), 3.74 (d, J = 11.1 Hz, 3H), 2.33 (s, 12H); 13C NMR (100 MHz, CDCl3) δ

138.2 (d, J = 13.8 Hz), 133.9 (d, J = 2.9 Hz), 130.9 (d, J = 135 Hz), 129.2 (d, J = 10.1

Hz), 51.4 (d, J = 6.0 Hz), 21.2; 31P NMR (162 MHz, CDCl3) δ 34.5.

Methyl Di(naphthalen-1-yl)phosphinate (3nb).

O

P OMe

White amorphous solid (60 mg, 90％):1H NMR (400 MHz, CDCl3) δ 8.59 (dd, J = 6.2,

3.4 Hz, 2H), 8.13 (dd, J = 15.8, 7.1 Hz, 2H), 8.03 (d, J = 8.2 Hz, 2H), 7.89−7.86 (m,

2H), 7.54−7.48 (m, 6H), 3.85 (d, J = 11.3 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ

134.1 (d, J = 10.4 Hz), 133.7, 133.6 (d, J = 3.1 Hz), 133.0 (d, J = 10.3 Hz), 128.9 (d, J

= 1.4 Hz), 127.5, 127.4 (d, J = 134 Hz), 126.5 (d, J = 4.8 Hz), 126.3, 124.6 (d, J =

15.0 Hz), 51.7 (d, J = 6.0 Hz); 31P NMR (162 MHz, CDCl3) δ 36.2; HRMS


Methyl Dibenzylphosphinate (3ob)2.


10H), 3.56 (d, J = 10.5 Hz, 3H), 3.08 (d, J = 16.4 Hz, 4H); 13C NMR (100 MHz,


S24

J = 3.1 Hz), 51.8 (d, J = 7.0 Hz), 35.6 (d, J = 87.0 Hz); 31P NMR (162 MHz, CDCl3) δ

49.2.

N-Hexyl-P,P-diphenylphosphinic Amide (5a)9.


7.53−7.37 (m, 6H), 2.94 (q, J = 7.7 Hz, 2H), 2.19 (br, 1H), 1.59−1.52 (m, 2H),

1.38−1.13 (m, 6H), 0.85 (t, J = 6.9 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 132.5 (d,

J = 130 Hz), 132.1 (d, J = 9.4 Hz), 131.8 (d, J = 2.6 Hz), 128.5 (d, J = 12.5 Hz), 40.8

(d, J = 1.7 Hz), 32.1 (d, J = 7.1 Hz), 31.4, 26.4, 22.5, 14.0; 31P NMR (162 MHz,

CDCl3) δ 23.6.

N-Phenethyl-P,P-diphenylphosphinic Amide (5b)10.


4H), 7.50−7.43 (m, 2H), 7.42−7.35 (m, 4H), 7.32−7.14 (m, 5H), 3.28−3.15 (m, 2H),

3.11−3.06 (m, 1H), 2.86 (t, J = 6.9 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 138.7,

131.7 (d, J = 122 Hz), 132.0 (d, J = 9.5 Hz), 131.6 (d, J = 2.9 Hz), 128.8, 128.41,

128.40, 126.3, 42.1 (d, J = 1.3 Hz), 38.3 (d, J = 7.1 Hz); 31P NMR (162 MHz, CDCl3)

δ 23.8.

N-Benzyl-P,P-diphenylphosphinic Amide (5c)11.


7.57−7.41 (m, 6H), 7.41−7.23 (m, 5H), 4.13 (t, J = 7.5 Hz, 2H), 3.50−3.44 (m, 1H);

13C NMR (100 MHz, CDCl3) δ 139.7 (d, J = 8.2 Hz), 132.2 (d, J = 129 Hz), 132.2 (d,

S25

J = 9.5 Hz), 131.9 (d, J = 2.7 Hz), 128.6 (d, J = 4.0 Hz), 128.5, 127.7, 127.4, 44.7; 31P

NMR (162 MHz, CDCl3) δ 23.8.

N-Isopropyl-P,P-diphenylphosphinic Amide (5d)12.


4H), 7.50−7.33 (m, 6H), 3.44−3.27 (m, 1H), 2.72 (br, 1H), 1.22 (d, J = 6.4 Hz, 6H);

13C NMR (100 MHz, CDCl3) δ 133.0 (d, J = 129 Hz), 132.1 (d, J = 9.4 Hz), 131.7 (d,

J = 2.6 Hz), 128.5 (d, J = 12.5 Hz), 43.8, 26.2 (d, J = 5.5 Hz); 31P NMR (162 MHz,

CDCl3) δ 21.9.

N-Cyclohexyl-P,P-diphenylphosphinic Amide (5e)13.


4H), 7.50−7.36 (m, 6H), 3.07−2.89 (m, 1H), 2.83−2.79 (m, 1H), 2.09−1.94 (m, 2H),

1.74−1.60 (m, 2H), 1.55−1.44 (m, 1H), 1.28−1.02 (m, 5H); 13C NMR (100 MHz,


J = 12.5 Hz), 50.6, 36.6 (d, J = 4.8 Hz), 25.3, 25.1; 31P NMR (162 MHz, CDCl3) δ

22.1.

N-(tert-Butyl)-P,P-diphenylphosphinic Amide (5f)14.


4H), 7.44−7.30 (m, 6H), 2.72 (br, 1H), 1.23 (s, 9H); 13C NMR (100 MHz, CDCl3) δ

134.9 (d, J = 128 Hz), 131.8 (d, J = 9.5 Hz), 131.4 (d, J = 2.7 Hz), 128.4 (d, J = 12.6

Hz), 53.2 (d, J = 3.2 Hz), 32.3 (d, J = 4.4 Hz); 31P NMR (162 MHz, CDCl3) δ 19.7.

S26

Diphenyl(pyrrolidin-1-yl)phosphine Oxide (5h)15.


7.49−7.32 (m, 6H), 3.15−2.99 (m, 4H), 1.90−1.72 (m, 4H); 13C NMR (100 MHz,


J = 12.4 Hz), 46.9 (d, J = 2.1 Hz), 26.6 (d, J = 6.7 Hz); 31P NMR (162 MHz, CDCl3) δ

25.4.

Morpholinodiphenylphosphine Oxide (5i)15.


7.54−7.42 (m, 6H), 3.77−3.63 (m, 4H), 3.17−2.99 (m, 4H); 13C NMR (100 MHz,

CDCl3) δ 132.4 (d, J = 9.1 Hz), 132.0 (d, J = 2.6 Hz), 130.8 (d, J = 129 Hz), 128.7 (d,

J = 12.4 Hz), 67.2 (d, J = 6.6 Hz), 45.0; 31P NMR (162 MHz, CDCl3) δ 29.2.

Diethyl Benzylphosphoramidate (5j)16.

Yellow oil (24 mg, 50％): 1H NMR (400 MHz, CDCl3) δ 7.60−7.54 (m, 4H),

7.53−7.48 (m, 1H), 4.45−4.15 (m, 6H), 3.04 (br, 1H), 1.54 (t, J = 7.0 Hz, 6H); 13C

NMR (100 MHz, CDCl3) δ 139.6 (d, J = 6.4 Hz), 128.5, 127.33, 127.28, 62.4 (d, J =

5.3 Hz), 45.3, 16.1 (d, J = 7.0 Hz); 31P NMR (162 MHz, CDCl3) δ 8.5.

Dibutyl Benzylphosphoramidate (5k).

S27

Yellow oil (18 mg, 30%): 1H NMR (400 MHz, CDCl3) δ 7.33−7.16 (m, 5H), 4.03 (d,

J = 9.7 Hz, 2H), 4.00−3.83 (m, 4H), 2.80 (br, 1H), 1.57 (dt, J = 14.6, 6.7 Hz, 4H),

1.39−1.27 (m, 4H), 0.86 (t, J = 7.4 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 139.6 (d,

J = 6.3 Hz), 128.5, 127.34, 127.28, 66.2 (d, J = 5.6 Hz), 45.4, 32.4 (d, J = 7.1 Hz),

18.8, 13.6; 31P NMR (162 MHz, CDCl3) δ 8.6; HRMS (ESI-Orbitrap) m/z: [M + Na]+

calcd for C15H26NO3PNa 322.1543, found 322.1539.

Diisopropyl Benzylphosphoramidate (5l)16.

Yellow amorphous solid (19 mg, 35％): 1H NMR (400 MHz, CDCl3) δ 7.33−7.19 (m,

5H), 4.69−4.49 (m, 2H), 4.05 (d, J = 9.1 Hz, 2H), 2.72 (br, 1H), 1.30 (d, J = 6.0 Hz,

6H), 1.25 (d, J = 6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 139.7 (d, J = 7.2 Hz),

128.5, 127.3(2C), 70.9 (d, J = 5.6 Hz), 45.4, 23.8 (d, J = 3.4 Hz), 23.7 (d, J = 4.0 Hz);

31P NMR (162 MHz, CDCl3) δ 6.6.

Diisobutyl Benzylphosphoramidate (5m).

Yellow amorphous solid (45 mg, 75%): 1H NMR (400 MHz, CDCl3) δ 7.36−7.18 (m,

5H), 4.08 (d, J = 9.9 Hz, 2H), 3.83−3.63 (m, 4H), 2.97 (br, 1H), 1.97−1.84 (m, 2H),

0.92 (d, J = 3.2 Hz, 6H), 0.90 (d, J = 2.8 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ

139.6 (d, J = 6.2 Hz), 128.5, 127.3, 127.2, 72.3 (d, J = 5.9 Hz), 45.3, 29.1 (d, J = 7.4

Hz), 18.7; 31P NMR (162 MHz, CDCl3) δ 8.4; HRMS (ESI-Orbitrap) m/z: [M + Na]+

calcd for C15H26NO3PNa 322.1543, found 322.1539.

References:

1. (a) H. R. Hays, J. Org. Chem., 1968, 33, 3690; (b) M. J. P. Harger and S.

Westlake, Tetrahedron, 1982, 38, 1511.

2. L. Deng, Y. Wang, H. Mei, Y. Pan and J. Han, J. Org. Chem., 2019, 84, 949.

S28

3. C. Li, T. Chen and L.-B. Han, Dalton Trans., 2016, 45, 14893.

4. Q.-Y. Li, T. R. Swaroop, C. Hou, Z.-Q. Wang, Y.-M. Pan and H.-T. Tang, Adv.

Synth. Catal., 2019, 361, 1761.

5. S. Li, T. Chen, Y. Saga and L.-B. Han, RSC Adv., 2015, 5, 71544.

6. B. Xiong, K. Zeng, S. Zhang, Y. Zhou, C.-T. Au and S.-F. Yin, Tetrahedron,

2015, 71, 9293.

7. Y. Li, Q. Yang, L. Yang, N. Lei and K. Zheng, Chem. Commun., 2019, 55, 4981.

8. Q. Chen, J. Zeng, X. Yan, Y. Huang, C. Wen, X. Liu and K. Zhang, J. Org.

Chem., 2016, 81, 10043.

9. A. Martínez-Asencio, D. J. Ramón and M. Yus, Tetrahedron, 2011, 67, 3140.

10. S. Wagner, M. Rakotomalala, Y. Bykov, O. Walter and M. Döring, Heteroatom

Chem., 2012, 23, 216.

11. T. C. Jankins, Z.-Y. Qin and K. M. Engle, Tetrahedron, 2019, 75, 3272.

12. I. Fernández, P. Oña-Burgos, G. Ruiz-Gómez, C. Bled, S. García-Granda and F.

López-Ortiz, Synlett, 2007, 611.

13. J. Xiao, Q. Su, W. Dong, Z. Peng, Y. Zhang and D. An, J. Org. Chem., 2017, 82,

9497.

14. V. Moodley, L. Mthethwa, M. N. Pillay, B. Omondi and W. E. van Zyl,

Polyhedron, 2015, 99, 87.

15. Y. Wang, P. Qian, J.-H. Su, Y. Li, M. Bi, Z. Zha and Z. Wang, Green Chem.,

2017, 19, 4769.

16. J. Fraser, L. J. Wilson, R. K. Blundell and C. J. Hayes, Chem. Commun., 2013, 49,

8919.

S29

6. NMR Spectra for Products

S30

S31

P

O

Ph

Ph

OMe

3ab

S32

O

PPh OnPr

Ph

3ac

O

PPh OnPr

Ph

3ac

S33

O

PPh OnPr

Ph

3ac

O

PPh OnBu

Ph

3ad

S34

O

PPh OnBu

Ph

3ad

O

PPh OnBu

Ph

3ad

S35

O

PPh OnAm

Ph

3ae

O

PPh OnAm

Ph

3ae

S36

O

PPh OnAm

Ph

3ae

O

PPh O

Ph

3af

Ph

S37

O

PPh O

Ph

3af

Ph

O

PPh O

Ph

3af

Ph

S38

O

PPh OBn

Ph

3ag

O

PPh OBn

Ph

3ag

S39

O

PPh OBn

Ph

3ag

O

PPh O

Ph

3ah

S40

O

PPh O

Ph

3ah

O

PPh O

Ph

3ah

S41

O

PPh O

Ph

3ai

O

PPh O

Ph

3ai

S42

S43

S44

O

PPh OCy

Ph

3ak

O

PPh OCy

Ph

3ak

S45

0.0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.98

3.08

11.0

7

19.9

3

9.92

2.98

1.01

6.02

4.00

0.82

0.84

0.85

0.86

0.86

0.87

0.89

0.91

0.93

0.95

0.95

0.96

0.97

0.98

0.98

1.00

1.01

1.03

1.04

1.04

1.06

1.07

1.08

1.10

1.11

1.12

1.13

1.18

1.19

1.20

1.21

1.22

1.23

1.25

1.28

1.31

1.32

1.33

1.33

1.34

1.41

1.42

1.49

1.50

1.51

1.52

1.54

1.57

1.59

1.60

1.62

1.63

1.64

1.65

1.66

1.68

1.71

1.91

1.92

1.94

1.95

7.40

7.41

7.41

7.42

7.42

7.43

7.44

7.45

7.47

7.48

7.49

7.49

7.50

7.51

7.51

7.78

7.78

7.78

7.80

7.80

7.80

7.81

7.81

7.81

7.83

7.83

O

PPh OCy

Ph

3ak

3alO

Me H

Me

H H

H

Me

Me

Me

P

O

Ph

Ph

S46

3alO

Me H

Me

H H

H

Me

Me

Me

P

O

Ph

Ph

3alO

Me H

Me

H H

H

Me

Me

Me

P

O

Ph

Ph

S47

O

PPh O

Ph

3an

O

PPh O

Ph

3an

S48

O

PPh O

Ph

3an

O

PPh O

Ph

3ao

OMe

S49

O

PPh O

Ph

3ao

OMe

O

PPh O

Ph

3ao

OMe

S50

O

PPh O

Ph

3ap

OMe

O

PPh O

Ph

3ap

OMe

S51

O

PPh O

Ph

3ap

OMe

O

PPh O

Ph

3aq

OMe

OMe

S52

O

PPh O

Ph

3aq

OMe

OMe

O

PPh O

Ph

3aq

OMe

OMe

S53

O

PPh O

Ph

3ar

Me

O

PPh O

Ph

3ar

Me

S54

O

PPh O

Ph

3ar

Me

O

PPh O

Ph

3as

Me

Me

S55

O

PPh O

Ph

3as

Me

Me

O

PPh O

Ph

3as

Me

Me

S56

O

PPh O

Ph

3at

Br

O

PPh O

Ph

3at

Br

S57

O

PPh O

Ph

3at

Br

O

PPh O

Ph

3au

Cl

S58

O

PPh O

Ph

3au

Cl

O

PPh O

Ph

3au

Cl

S59

O

PPh O

Ph

3av

O

PPh O

Ph

3av

S60

O

PPh O

Ph

3av

O

PPh O

Ph

O

PPh O

Ph15:13aw

OH

OH

HO OH

S61

O

PPh O

Ph

O

PPh O

Ph15:13aw

OH

OH

HO OH

O

PPh O

Ph

O

PPh O

Ph15:13aw

OH

OH

HO OH

S62

O

P OMe

3bb

MeO

OMe

O

P OMe

3bb

MeO

OMe

S63

O

P OMe

3bb

MeO

OMe

O

P OMe

3cb

Me

Me

S64

O

P OMe

3cb

Me

Me

O

P OMe

3cb

Me

Me

S65

O

P OMe

3db

Ph

Ph

O

P OMe

3db

Ph

Ph

S66

S67

S68

O

P OMe

3fb

F

F

O

P OMe

3fb

F

F

S69

O

P OMe

3fb

F

F

O

P OMe

3gb

F3C

CF3

S70

O

P OMe

3gb

F3C

CF3

O

P OMe

3gb

F3C

CF3

S71

S72

S73

O

P OMe

3ib

Me

Me

O

P OMe

3ib

Me

Me

S74

O

P OMe

3jb

F

F

O

P OMe

3jb

F

F

S75

O

P OMe

3jb

F

F

O

P OMe

3kb

Me

Me

S76

O

P OMe

3kb

Me

Me

O

P OMe

3kb

Me

Me

S77

O

P OMe

3lb

MeO

OMe

MeO

MeO

O

P OMe

3lb

MeO

OMe

MeO

MeO

S78

O

P OMe

3lb

MeO

OMe

MeO

MeO

S79

S80

O

P OMe

3nb

O

P OMe

3nb

S81

O

P OMe

3nb

O

P OMe

3ob

Bn

Bn

S82

O

P OMe

3ob

Bn

Bn

O

P OMe

3ob

Bn

Bn

S83

O

PPh NH

Ph5a

nBu

O

PPh NH

Ph5a

nBu

S84

O

PPh NH

Ph5a

nBu

O

PPh NH

Ph5b

Ph

S85

O

PPh NH

Ph5b

Ph

O

PPh NH

Ph5b

Ph

S86

O

PPh NH

Ph5c

Bn

O

PPh NH

Ph5c

Bn

S87

O

PPh NH

Ph5c

Bn

O

PPh NH

Ph5d

iPr

S88

O

PPh NH

Ph5d

iPr

O

PPh NH

Ph5d

iPr

S89

O

PPh NH

Ph5e

Cy

O

PPh NH

Ph5e

Cy

S90

O

PPh NH

Ph5e

Cy

O

PPh NH

Ph5f

tBu

S91

O

PPh NH

Ph5f

tBu

O

PPh NH

Ph5f

tBu

S92

O

PPh N

Ph5h

O

PPh N

Ph5h

S93

O

PPh N

Ph5h

O

PPh N

Ph5i

O

S94

O

PPh N

Ph5i

O

O

PPh N

Ph5i

O

S95

O

PEtO NH

OEt5j

Bn

O

PEtO NH

OEt5j

Bn

S96

O

PEtO NH

OEt5j

Bn

O

PnBuO NH

OnBu5k

Bn

S97

O

PnBuO NH

OnBu5k

Bn

O

PnBuO NH

OnBu5k

Bn

S98

O

PiPrO NH

OiPr5l

Bn

O

PiPrO NH

OiPr5l

Bn

S99

O

PiPrO NH

OiPr5l

Bn

O

PiBuO NH

O iBu5m

Bn

S100

O

PiBuO NH

O iBu5m

Bn

O

PiBuO NH

O iBu5m

Bn

Documents

Phosphoryl radical-initiated Atherton–Todd-type …S1 Phosphoryl radical-initiated Atherton–Todd-type reaction under open air Yingcong Ou,a Yuanting Huang,a Zhenlin He,a Guodian